以腐植酸钾(KHA)、壳聚糖(CTS)、蒙脱土(MMT)为原料合成了一种KHA/CTS/AA-MMT水凝胶材料, 用于去除重金属Cu(Ⅱ)和Cr(Ⅵ)。采用SEM、FT-IR、XPS对水凝胶材料结构进行表征, 证实水凝胶的空间网络结构。对水凝胶材料的吸水倍率, 以及在不同pH条件进行测试, 发现在弱酸性至碱性吸水溶胀性能优良, 溶胀率可达80g/g。研究结果表明, 在298K时, 水凝胶材料对Cu(Ⅱ)和Cr(Ⅵ)的吸附量分别可达249.45和212.81mg/g;通过热力学分析可知, 水凝胶对Cu(Ⅱ)、Cr(Ⅵ)的吸附是放热过程, 主要是化学吸附且为自发过程。通过XPS与吸附过程理论拟合得知, 吸附Cu(Ⅱ)、Cr(Ⅵ)主要是羰基的螯合与氨基的配位作用, 该材料在重金属去除方面具有广阔的应用前景。
A KHA/CTS/AA-MMT hydrogel material was synthesized using potassium humate (KHA), chitosan (CTS) and montmorillonite (MMT) as raw materials for the removal of heavy metals Cu(Ⅱ) and Cr(Ⅵ).SEM, FT-IR, and XPS were used to characterize the structure of the hydrogel material, and the spatial network structure of the hydrogel was confirmed.The water absorption rate of the hydrogel material was tested under different pH conditions, and it was found that it had excellent water absorption and swelling performance from weak acidic to alkaline conditions, with a swelling rate of up to 80g/g.The research results showed that:at 298K, the adsorption capacity could reach 249.45mg/g and 212.81mg/g, respectively.The thermodynamic analysis showed that the adsorption of Cu(Ⅱ) and Cr(Ⅵ) by hydrogel was an exothermic process, mainly chemical adsorption and spontaneous process.According to XPS analysis and theoretical fitting of the adsorption process, the adsorption of Cu(Ⅱ) and Cr(Ⅵ) was mainly achieved by the coordination of the carbonyl group and the amino group.This material has broad application prospects in the removal of heavy metals.
[1] Wang R S,Liang R H,Dai T T,et al.Pectin-based adsorbents for heavy metal ions:a review[J].Trends in Food Science & Technology,2019,91:319-329.
[2] Shabbah B,Nor Y Y,Noorashikin M S,et al.Review of chitosan composite as a heavy metal adsorbent:material preparation and properties[J].Carbohydrate Polymers,2021,259:117613.
[3] Perumal S,Atchudan R,Edison T N J I,et al.A short review on recent advances of hydrogel-based adsorbents for heavy metal ions[J].Metals,2021,11(6):864.
[4] Elham J,Reza A G,Arvin H,et al.Tough dual-network GAMAAX hydrogel for the efficient removal of cadmium and nickle ions in wastewater treatment applications[J].Journal of Industrial and Engineering Chemistry,2020,94:352-360.
[5] Zhu F,Zheng Y M,Zhang B G,et al.A critical review on the electrospun nanofibrous membranes for the adsorption of heavy metals in water treatment[J].Journal of Hazardous Materials,2021,401:123608.
[6] Sun Y J,Zhou S B,Sun W Q,et al.Flocculation activity and evaluation of chitosan-based flocculant CMCTS-g-P(AM-CA) for heavy metal removal[J].Separation and Purification Technology,2020,241:116737.
[7] Li J,Qiu C,Fan H B,et al.A novel cyclodextrin-functionalized hybrid silicon wastewater nano-adsorbent material and its adsorption properties[J].Molecules (Basel,Switzerland),2018,23(6):1485.
[8] Kim Y,Kim I,Lee T S,et al.Porous hydrogel containing Prussian blue nanoparticles for effective cesium ion adsorption in aqueous media[J].Journal of Industrial and Engineering Chemistry,2018,60:465-474.
[9] Zaimee M Z A,Sarjadi M S,Rahman M L.Heavy metals removal from water by efficient adsorbents[J].Water,2021,13(19):2659.
[10] 黄良仙,韩星星,牛育华,等.聚乙烯醇/海藻酸钠双交联凝胶球的制备及其应用[J].精细化工,2021,38(7):1459-1472.
[11] Moon S,Jang S W,Kim Y,et al.Prussian blue decorated hydrogel particles for effective removal of cesium ion from aqueous media[J].Polymer,2020,186:12209.
[12] Stdipta P,Samuel H,Wang C.EDTA-inspired polydentate hydrogels with exceptionally high heavy metal adsorption capacity as reusable adsorbents for wastewater purification[J].ACS Applied Materials & Interfaces,2020,12(22):25276-25285.
[13] Li S Z,Li Y P,Fu Z,et al.A ‘top modification’ strategy for enhancing the ability of a chitosan aerogel to efficiently capture heavy metal ions[J].Journal of Colloid and Interface Science,2021,594:141-149.
[14] 冯江涛,王桢钰,闫炫冶,等.吸附去除水体重金属离子的影响因素研究进展[J].西安交通大学学报,2022(2):1-17.
[15] Simeone C,Angelo F,Pasquale I,et al.Sorption of organic pollutants by humic acids:a review[J].Molecules,2020,25(4):918.
[16] Deng C H,Hou L J,Zhang C F.Eco-friendly ferrimagnetic-humic acid nanocomposites as superior magnetic adsorbents[J].Materials,2021,14(18):5125.
[17] Yu Y Q,Liu M,Yang J Y.Characteristics of vanadium adsorption on and desorption from humic acid[J].Chemistry and Ecology,2018,34(6):548-564.
[18] Karthik R,Swatantra P S,Christopher J A,et al.An environmentally-friendly chitosan-lysozyme biocomposite for the effective removal of dyes and heavy metals from aqueous solutions[J].Carbohydrate Polymers,2018,199:506-515.
[19] Li D W,Tian X J,Wang Z Q.Multifunctional adsorbent based on metal-organic framework modified bacterial cellulose/chitosan composite aerogel for high efficient removal of heavy metal ion and organic pollutant[J].Chemical Engineering Journal,2020,383:123127.
[20] Tang S X,Yang J Y,Lin L Z,et al.Construction of physically crosslinked chitosan/sodium alginate/calcium ion double-network hydrogel and its application to heavy metal ions removal[J].Chemical Engineering Journal,2020,393:124728.
[21] Lin Z K,Yang Y R,Liang Z Z,et al.Preparation of chitosan/calcium alginate/bentonite composite hydrogel and its heavy metal ions adsorption properties[J].Polymers,2021,13(11):1891.
[22] Antuzevics A,Krieke G,Ozols H,et al.Oxidation state and local structure of chromium ions in LaOCl[J].Materials (Basel,Switzerland),2021,14(13):3539.
[23] Niu J J,Yan W J,Zhang W,et al.Potential-responsive ions-selectively capture effect for efficient removal of copper ions from wastewater[J].Electrochimica Acta,2020,330:135249.
基金资助
陕西省重点研发计划(2022NY-195);西安市创新能力强基计划-(4)农业技术研发项目(21NYYF0025);陕西省科技厅一般项目(2020SF-416)
PDF
